Pesticides

ABSTRACT

New pesticidal compositions which comprise 
     at least one signal substance, 
     at least one UV absorber which is only sparingly miscible with water, 
     at least one unsaturated oil which is only sparingly miscible with water and, 
     if desired, pesticidally active compounds and/or additives, 
     a process for the preparation of the new compositions, and their use for controlling insects and undesirable representatives of the order Acarina.

The present invention relates to novel compositions for controllingharmful insects and representatives of the order Acarina, a process forthe preparation of these compositions, and their use in agriculture,forestry and horticulture.

When controlling phytophagous animal pests with the aid of pesticides,one attempts to minimize contamination of the plants to be protected andtheir environment, including the soil in which they grow. Moreover,beneficial animals and warm-blooded species are to be adversely affectedby the pesticidally active compounds as little as possible. However, incontrast, the pests to be controlled are to be exposed to thepesticidally active compounds as much as possible so that the pests cantake up sufficient amounts of the active compounds by contact action, asstomach poisons or via the gas phase.

When controlling insects, the abovementioned conditions can be met forexample by combining signal substances such as pheromones, kairomones orattractants, which have an attractant action on insects, withinsecticidally active compounds and applying the resulting mixtures tothe stand to be protected not in such a way that the entire area iscovered, but only locally to sharply defined individual sites. Since thesignal substances are released at the treated sites, the pests migrateto these sites, become contaminated with the pesticidally activecompounds and are destroyed. This type of insect control is termed the“attract-and-kill” method.

In contrast, it is also possible to control insects with the aid of theso-called “confusion” strategy. When using this method, the amount ofpheromones introduced into the plant stand to be protected is so largethat the male insects are no longer capable of locating the femaleinsects. This prevents the pests from breeding.

For the compositions used in the two control strategies to develop asufficiently long-term action, the formulations in question mustcomprise the attractants in such a form that, on the one hand, they canbe released in a controlled manner but, on the other hand, are protectedagainst environmental factors such as light, oxygen and the weather.

A large number of preparations based on the above-described principlesof controlling animal pests have already been disclosed. One attempts toprotect the sensitive active compounds against undesirable degradationby means of a variety of measures.

For example, EP-A 0 055 475 discloses that male insects of the speciesCossus cossus can be controlled with the aid of (Z)-5-dodecen-1-ylacetate, if appropriate in the form of a mixture with (Z)-3-decen-1-ylacetate, (Z)-3-dodecen-1-yl acetate and/or (E)-5-dodecen-1-yl acetate.The attractant, or the mixtures of the active components, are applied insolvents which have a low vapour pressure, such as oils or fats, orelse, if appropriate, as a mixture with antioxidants and UV stabilizersin the form of an adsorbate on inert solids.

Furthermore, GB-PA 2 064 323 describes insecticides based on pheromonesin which the signal :substances and UV stabilizers and additionaladditives such as antioxidants are fixed onto a combination of absorbingand adsorbing solids. However, the disadvantage of these preparations istheir relatively poor resistance to weathering despite the stabilizingadditives which they comprise and the fact that the active compounds aretherefore decomposed or leached out after a relatively short time.

Furthermore, it has already been disclosed to employ combinations ofattractants and insecticides for pest control in microencapsulated formor bound in water-soluble polymers (cf. JP-A 59-7101 and “Advances inPesticide Formulation Technology” 1984, Chapter 11, pages 151-162). Inthe preparation of these microcapsules, a procedure is followed in whichthe active compounds are dissolved in an oil phase, the resultingmixture is emulsified in water and the emulsion is subsequentlyencapsulated. Controlled release of the attractant and, in addition, itsprotection against environmental factors are thereby achieved. Thedisadvantage of this process is, however, the complicatedmicroencapsulation process. Moreover, the attractants are not alwayssufficiently stabilized against environmental factors, despite theencapsulation, because the thin capsule wall does not provide sufficientprotection against photochemical degradation.

According to GB-A 2 141 932, preparations which comprise pheromones, ifappropriate as a mixture with UV absorbers and other additives, inliquid or semi-liquid, liquid, water-resistant polymers which protectagainst UV radiation, can be used as pesticides. While the activecomponents remain stable over a sufficiently long period in theseformulations, the amount of active compound which diffuses out does notalways guarantee a sufficiently high degree of efficacy.

EP-A 0 376 888 discloses that formulations which are composed mostly ofone or more permanently liquid UV absorbers, besides insecticides andattractants and customary additives, and which are present in viscousform which remains permanently uncured are also suitable for controllingpests. The very high content of UV-absorbing substances protects theattractants in these formulations against photodegradation over aprolonged period. However, the use under realistic conditions causesproblems since the UV absorbers are, as a rule, highly stable and arenot degraded, or are degraded only very slowly. If the formulation isapplied regularly over several years, it is therefore accumulated in thearea under cultivation which has been treated.

Furthermore, WO 87-04 591 discloses compositions for controlling spidermites. The formulations are composed of a substrate which comprisesattractants such as Nerodiol and Farnesol, furthermore insecticidallyactive compounds and also oils which are added in the form of emulsions.The attractants are released from these substrates in a controlledmanner. However, the disadvantage is that no long-term action isachieved when using these compositions. Rather, achieving satisfactorycontrol requires regular subsequent treatments.

J. Entomol. Sci. Vol. 25, No. 4, 581-586, (1990) describes pheromone—andinsecticide—comprising preparations for controlling the cotton bollweevil (Anthonomus grandis). As an essential component, the compositionscomprise cotton seed oil, which promotes feeding of the pest andtherefore has a beneficial effect on the uptake of active compound.However, the fact that this vegetable oil does not contribute tostabilizing the formulation against environmental effects isunfavourable.

Finally, it has been disclosed that oils in attractant-comprisingpreparations can act as solvents for active compounds (cf. WO 87-04 591,EP-A 0 055 475 and “Advances in Pesticide Formulation Technology 1984,Chapter 11, pages 151 to 162). The active compounds, however, are notstabilized against undesirable degradation.

There have now been found new pesticidal compositions which comprise

at least one signal substance,

at least one UV absorber which is only sparingly miscible with water,

at least one unsaturated oil which is only sparingly miscible with waterand

if appropriate, pesticidally active compounds and/or additives.

Furthermore, it has been found that compositions according to theinvention can be prepared by

a) dispersing at least one signal substance, at least one UV absorberwhich is only sparingly miscible with water and, if appropriate,pesticidally active compounds and/or additives in at least oneunsaturated oil which is only sparingly miscible with water and

b) if appropriate, emulsifying this premix in water while addingsurface-active substances.

Finally, it has been found that the compositions according to theinvention are highly suitable for controlling harmful insects andundesirable representatives from the order Acarina in agriculture,forestry and horticulture.

It must be considered as extremely surprising that the compositionsaccording to the invention, which comprise a mixture of UV absorber andunsaturated oil, protect the signal substances which are present and thepesticidally active compounds which may also be present, better againstenvironmental degradation than prior-art compositions which compriseeither only the unsaturated vegetable oil or merely the UV absorber.

The compositions according to the invention are distinguished by aseries of advantages. For example, they allow specific andenvironmentally friendly pest control over a prolonged period.Furthermore, the attractants in these preparations are extremely stableeven under unfavourable weather conditions.

The signal substances which may be present in the compositions accordingto the invention are all customary substances which have an attractantaction on the pests to be controlled and which alter the behaviour ofthe latter. Signal substances which are preferably suitable arepheromones, kairomones and attractants. Examples of such substanceswhich may be mentioned are the following:

Z-5-Decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate,E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate,Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate,11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9,11-dodecadienylacetate, Z-11-tridecenyl acetate, E-11-tridecenyl acetate, tetradecenylacetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate,E-8-tetradacenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenylacetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate,Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z-12-pentadecenylacetate, E-12-pentadecenyl acetate, hexadecanyl acetate, Z-7-hexadecenylacetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanylacetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate,E,E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate,E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate,E,Z-4,7-tri-decadienyl acetate, 4-methoxy-cinnamaldehyde, β-ionone,estragol, eugenol, indole, 8-methyl-2-decyl propanoate,E,E-9,11-tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate,Z,Z-7,11-hexadecadienyl acetate, E,Z-7,11-hexadecadienyl acetate,Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate,Z,E-3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate,E,E-3,13-octadecadienyl acetate, ethanol, hexanol, heptanol, octanol,decanol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol,Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol,E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol,Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol,E,Z-8,10-dodecadienol, Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol,E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol,Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol,Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol,Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol,Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol,Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol,(E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol,E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal,Z-9-dodecenal, tetradecanal, Z-7-tetradecenal, Z-9-tetradecenal,Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal,E,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal,Z,E-9,12-tetradecadienal, hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal,Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal,Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8-hexadecenal,(E)-14-methyl-8-hexadecenal, Z,Z-7,11-hexadecadienal,Z,E-7,11-hexadecadienal, Z,E-9,11-hexadecadienal,E,E-10,12-hexadecadienal, E,Z-10,12-hexadecadienal,Z,E-10,12-hexadecadienal, Z,Z-10,12-hexadecadienal,Z,Z-11,13-hexadecadienal, octadecanal, Z-11-octadecenal,E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3-methyl butanoatedisparlure: (+) cis-7,8-epoxy-2-methyloctadecane, seudenol:3-methyl-2-cyclohexen-1-ol, sulcatol: 6-methyl-5-hepten-2-ol, ipsenol:2-methyl-6-methylene-7-octen-4-ol, ipsdienol:2-methyl-6-methylene-2,7-octadien-4-ol, grandlure I:cis-2-isopropenyl-1-methylcyclobutane-ethanol, grandlure II:Z-3,3-dimethyl-1-cyclohexane-ethanol, grandlure III:Z-3,3-dimethyl-1-cyclohexane-acetalde-hyde, grandlure IV:E-3,3-dimethyl-1-cyclohexane-acetaldehyde, cis-2-ver-benol:cis-4,6,6-trimethylbicyclo[3,1,1]hept-3-en-2-ol cucurbitacin,2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, cucurbitacin,2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, α-pinene:2,6,6-trimethylbicyclo[3,1,1]hepten-2-ene, α-caryophyllene:4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane, Z-9-tricosene,(α-multistriatin,2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane,methyleugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, lineatin:3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane, chalcogran:2-ethyl-1,6-dioxaspiro[4,4]nonane, frontalin:1,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane, endo-brevicomin:endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, exo-brevicomin:exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane,(Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, farnesol:3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, nerolidol3,7-11-trimethyl-1,6,10-dodecatrien-3-ol,3-methyl,6-(1-methylethenyl)-9-decen-1-ol acetate,(Z)-3-methyl-6-(1-methylethenyl)-3,9-decadien-1-ol acetate,(E)-3,9-methyl-6-(1-methyl-ethenyl)-5,8-decadien-1-ol acetate,3-methylene-7-methyl-octen-1-ol propionate,(Z)-3,7-dimethyl-2,7-octadien-1-ol propionate,(Z)-3,9-dimethyl-6-(1-methyl-ethenyl)-3,9-decadlien-1-ol propionate.

The compositions according to the invention comprise at least one UVabsorber which is only sparingly miscible with water. These are to beunderstood as meaning substances which are capable of absorbing UVlight, preferably UV radiation from surlight in a wavelength range offrom 270 to 400 nm. Suitable substances are preferably liquid UVabsorbers, such as

2-(2-hydroxyphenyl)-benzotriazoles of the formula

 in which

a R¹ represents hydrogen or chlorine,

R² represents hydrogen, alkyl, phenylalkyl or phenyl and

R³ represents alkyl, phenylalkyl, phenyl or —(CH₂)₂—COO-alkyl,

2-hydroxy-4-alkoxy-benzophenones of the formula

 in which

R⁴ represents hydrogen, alkyl or alkoxy and

R⁵ represents alkyl, preferably isooctyl or dodecyl,

oxalanilides of the formula

 in which

R⁶ represents alkyl,

cinnamic acid derivatives of the formula

 in which

R⁷ represents alkyl, preferably n-butyl, or

 in which

 R⁸ and R⁹ represent alkyl, or

 in which

R¹⁰ represents alkyl, preferably butyl or the radical

and

triazine derivatives of the formula

 in which

R¹¹ represents hydrogen or hydroxyl,

R¹² represents alkyl having 1 to 18 carbon atoms,

R¹³ represents alkyl having 1 to 18 carbon atoms or alkoxy having 1 to18 carbon atoms,

R¹⁴ represents alkyl having 1 to 18 carbon atoms and

m and n represent the numbers 0, 1 or 2.

Examples of 2-(2-hydroxyphenyl)-benzotriazoles of the formula (I) whichmay be mentioned are the substances listed in Table 1 below:

TABLE 1 (I)

Trade name R¹ R² R³ Tinuvin 109 Cl —C(CH₃)₃ 50%

50%

Tinuvin 171 H —C₁₂H₂₅-(iso- —CH₃ or C₂-C₁₂-alkyl mer mixture Tinuvin1130 H —(CH₃)₃ approx. 50 %

approx. 38 %

approx. 12% polyethylene glycol (EO 300) “SL 874” H —C(CH₃)₃

The compositions according to the invention comprise at least oneunsaturated oil which is sparingly miscible with water. These are to beunderstood as meaning all straight-chain or branched oily liquids ofsynthetic or natural origin which optionally contain functional groupsand which have one or more unsaturated bonds between two carbon atomsand whose solubility in water is <1 g/l.

Unsaturated oils are preferably of vegetable or animal origin and aredistinguished by a high content of unsaturated fatty acids. Examples ofsuch oils are linseed oil, palm oil, groundnut oil, cotton oil, soyaoil, sunflower oil, colza oil, castor oil and fish oil. Castor oil isparticularly preferred. However, the fatty acids contained in theabovementioned oils, or compounds which are obtained by chemicallymodifying the fatty acids such as, for example, fatty acid ethoxylates,can also be used to prepare the compositions according to the invention.Examples of such fatty acids which can be employed individually or inthe form of a mixture are myristoleic acid, palmitoleic acid, oleicacid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid,linolenic acid, arachidonic acid and clupanodonic acid.

The compositions according to the invention can comprise one or morepesticidally active compounds. These are to be understood as meaning allcustomary substances which are suitable for controlling harmful insectsand undesirable representatives of the order Acarina. The following arepreferably suitable: carbamates, organophosphorus compounds,nitrophenols and their derivatives, nitromethylenes, nicotinoids,formamidines, ureas, phenylbenzoylureas, pyrethroids, chlorinatedhydrocarbons and Bacillus thuringiensis preparations. Examples which maybe mentioned are the following substances:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,betacyfluthrin, bifenthrin, BPMC, bromfenprox, bromophos A, bufencarb,buprofezin, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos; dioxathion, disulfoton,

edifenphos, emainectin, esfenvalerate, ethiofencarb, ethion,ethofenprox, ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycl.oxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazophos, isofenphos, isoprocarb, isoxathion, ivermectin,lambda-cyhalothrin., lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, rnethidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, mnxidectin,

naled, NC 184, NI 25, nitenpyram

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen, quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozid, tebu:Fenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathene, triazophos, triazuron, trichlorfon, triflumuron,trimelthacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

Suitable additives which may be present in the compositions according tothe invention are all those substances which can conventionally beemployed as additives in plant treatment products. They includepolymers, surface-active substances, colourants, antioxidants,thickeners, fillers, antifreeze agents and solvents. Moreover, thecompositions according to the invention can also contain water.

Suitable polymers which can be present in the compositions according tothe invention are all customary polymers or copolymers which are solubleor dispersible in water. Preferably suitable are polymers which areaccessible by synthesis by means of anionic or non-ionic polymerizationof suitable monomers, for example by emulsion polymerization or beadpolymerization with the aid of free-radical formers or other initiatorsystems. Other polymers which can preferably be employed are those basedon natural-rubber latices.

Examples of particularly prefered polymers which may be mentioned arethe following substances:

Polyvinyl acetate (Mowilith®), polyvinyl alcohols with different degreesof hydrolysis (Mowiol®), polyvinylpyrrolidones (Lewiskod K®, Agrimer®),polyacrylates (Carbopol®), acrylate-, polyol- or polyester-based paintsystem binders which are soluble or dispersible in water (Desmophen®,Roskydal®, Bayhydrol® polyraers which may be mentioned are the followingsubstances:), moreover copolymers of two or more monomers such asacrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaricacid, maleic anhydride, vinylpyrrolidone, ethylenically unsaturatedmonomers such as ethylene, butadiene, isoprene, chloroprene, styrene,divinylbenzene, ot-methylstyrene or p-methylstyrene, further vinylhalides such as vinyl chloride and vinylidene chloride, additionallyvinyl esters such as vinyl acetate, vinyl propionate or vinyl stearate,moreover vinyl methyl ketone or esters of acrylic acid or methacrylicacid with monohydric alcohols or polyols such as methyl acrylate, methylmethacrylate, ethyl acrylate, ethylene methacrylate, lauryl acrylate,lauryl methacrylate, decyl acrylate, N,N-dimethylamino-ethylmethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylateor glycidyl methacrylate, furthermore diethyl esters or monoesters ofunsaturated dicarboxylic acids, furthermore (meth)acrylamido-N-methylolmethyl ether, amides or nitriles such as acrylamide, methacrylamide,N-methylol(meth)acrylamide, acrylonitrile, methacrylonitrile, and alsoN-substituted maleiraides and ethers such as vinyl butyl ether, vinylisobutyl ether or vinyl phenyl ether.

Suitable surface-active substances which can be present in thecompositions according to the invention are all those substances whichhave surface-active properties and which are conventionally used inplant treatment products. Preferably suitable are non-ionic and anionicemulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, alkylaryl polyglycol ethers, fatty amineethoxylates, alkylsulphonates, alkyl sulphates, alkylarylsulphonates,aryl sulphates and silicone surfactants. Examples of such surface-activesubstances are listed in McCutcheon's “Emulsifiers and Detergents” 1982North America Edit, MC Publishing Co., 175 Rock Road, Glen Rock, N.J. 07452, USA.

Suitable colourants are soluble or sparingly soluble colour pigmentssuch as, for example, titanium dioxide, colour black or zinc oxide.

Suitable antioxidants are all substances which can usually be employedfor this purpose in plant treatment products. Sterically hinderedphenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes arepreferred.

Suitable thickeners are all substances which can usually be employed forthis purpose in plant treatment products. The following are preferablysuitable: organic polymers such as partially or fully neutralizedpolyacrylic acids (Carbopol®), polyvinylpyrrolidone homo- or copolymers(Luviskol K® or Luviskol VA®), polyethylene glycols (Polyox®), ethyleneoxide/propylene oxide copolymers (Pluronic®), polyvinyl alcohols andnon-ionically or ionically modified celluloses (Tylose®), thixotropicxanthan-based thickeners (Kelzan®), and moreover inorganic dispersethickeners such as precipitated or pyrogenic silicas, kaolins,bentonites, aluminium/silicon mixed oxides, and silicates.

Suitable antifreeze agents are all substances which can usually beemployed for this purpose in plant treatment products. Urea, glycerol orpropylene glycol are preferably suitable.

Suitable fillers are, again, all inert materials which can usually beemployed for this purpose in plant treatment products. The following arepreferably suitable: ground minerals, calcium carbonate, ground quartzand aluminium/silicon mixed oxides or mixed hydroxides.

Suitable solvents are all inert, organic solvents which can usually beemployed for this purpose in plant treatment products. Preferredsubstances are glycols such as propylene glycol and polyethylene glycolshaving various molecular weights; ketones such as methyl isobutylketone, methyl isopropyl ketone and cyclohexanone; amides such asdimethyl- or diethyl formamide; N,N-dialkylated carboxamides (forexample Hallcomid®); alkyllactams such as substituted pyrrolidones (forexample N-methylpyrrolidone and Surfadone®) and caprolactams (forexample Azone®); hydrocarbons, n-paraffins and isoparaffins havingvarious boiling ranges as can be obtained, for example, under the tradenames Exxol®, Norpar® and Isopar®; aromatic hydrocarbons such as xyleneand aromatic distillation fractions (for example Solvesso®); esters suchas propylene glycol monomethyl ether acetate, dibutyl adipate anddi-n-butyl phthalate; ethers such as propylene glycol methyl ether orpropylene glycol butyl ether; alcohols such as ethanol, n- andi-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol,tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, and higher alcohols,furthermore liquid carriers which have been obtained by modifyingvegetable oils, such as, for example, rapeseed oil methyl ester and2-ethylhexyl laurate; and furthermore dimethyl sulphoxide, dioxane andtetrahydrofuran. The solvents can be employed in the form of individualcomponents or in the form of mixtures. Particularly preferred are thosewhich are miscible with the UV stabilizer or the unsaturated oil andwhich are not unduly volatile.

The concentrations of individual components in the compositionsaccording to the invention can be varied within a wide range. Forexample, after deducting the water which is optionally present in thecompositions according to the invention, the concentrations

of signal substances are generally between 0.01 and 1% by weight,preferably between 0.05 and 0.3% by weight,

of UV absorbers are generally between 1 and 40% by weight, preferablybetween 5 and 20% by weight,

of unsaturated oils are between 10 and 90% by weight, preferably between40 and 85% by weight,

of pesticidally active compounds are generally between 0 and 10% byweight, preferably between 0 and 5% by weight,

of additives are between 0 and 70% by weight, preferably between 0 and60% by weight.

Besides, the compositions according to the invention can also comprisewater. The water content prior to drying varies within a wide range. Itis generally between 0 and 80% by weight.

When preparing the compositions according to the invention, a procedureis generally followed in which a premix is first prepared by dissolvingor dispersing at least one signal substance, at least one UV absorberand, if appropriate, one or more pesticidally active compounds in atleast one unsaturated oil with stirring at temperatures between 20° C.and 70° C., preferably at room temperature, and, if appropriate,additives are added. However, a different procedure may also be followedwhen preparing compositions according to the invention. For example, thepremix can be dispersed in a solution of at least one surface-activesubstance in water with stirring at temperatures between 20° C. and 70°C., preferably at room temperature. The dispersing process can becarried out in such a way that an oil-in-water emulsion is formed inwhich the average particle size is generally between 0.5 and 50 μm, butpreferably between 1 and 20 μm. The resulting emulsion can subsequentlybe treated with a solution or dispersion of at least one polymer inwater and, if appropriate, additives with stirring at temperaturesbetween 20° and 70° C., but preferably at room temperature.

However, a different procedure may be followed when preparing thecompositions according to the invention. In principle, it is possible tomix the components in any order. All stirring and mixing apparatus whichis customary for this purpose is suitable for preparing the compositionsaccording to the invention.

The compositions according to the invention are obtained from thepreparation in a fluid or viscous state. Depending on the preparationprocess, they remain viscous after application or else form anon-flowable coating.

The compositions according to the invention are highly suitable forcontrolling harmful insects and undesirable representatives of the orderAcarina which are found in agriculture, in forests and in horticulture,including viticulture. For example, they can be employed against thepests mentioned below.

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order cf the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonivchus spp. and Tetranychusspp.

Using conventional devices as they are known to those skilled in the artthe compositions according to the invention can be applied to, anddistributed on, the areas under cultivation or plants to be treated inthe form of droplets, the drop-size range or thin limited layers.Particularly suitable for the treatment of orchard crops or grape vinesis a process in which a defined amount of the formulations according tothe invention is applied to the stems of the plants with the aid ofdosing dispensers, pipettes or syringes, it being possible for theapplication device also to be provided with a spreading device or abroad-jet nozzle so as to apply the compositions broadly over arelatively large area. It is also possible to spread the formulationsaccording to the invention on a solid support, where they are allowed todry.

The amounts in which the compositions according to the invention areapplied can vary within a substantial range. They are in general in theorder of magnitude which is conventionally used for “attract-and-kill”formulations.

The preparation and the use of compositions according to the inventionis illustrated by the examples which follow.

PREPARATION EXAMPLES Examples 1 to 5

The pheromone E,E-8,10-dodecadienol (=pheromone), the UV absorber2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate (=UV absorber A) and theUV absorber 2-hydoxy-4-methoxy-benzophenone (=UV absorber B) aredissolved with stirring at 50° C. in a 0.2% by weight solution ofbutylhydroxytoluene in castor oil (oil solution) in the amounts listedin Table 2

TABLE 2 Ex. Pheromone UV absorber A UV absorber B Oil solution No. (g)(g) (g) (g) 1 2 12.5 12.5 73.0 2 2 10.0 10.0 78.0 3 2 7.5 7.5 83.0 4 25.0 5.0 88.0 5 2 2.5 2.5 93.0

Example 6

2 g of the pheromone E,E-8,10-dodecadienot and 25.0 g of thebenzotriazole of the formula

are dissolved at room temperature with stirring in 73 g of a 0.2% byweight solution of butylhydroxytoluene in castor oil.

Pheromone Stability Assessment

In each case 1 g of the formulations according to the invention ofExamples 1 to 6 were placed into a round glass container of diameter 5cm and covered with a sheet of quartz glass. In a Heraeus “Suntest CPS”rapid-exposure apparatus, the containers were exposed to light over aperiod of 6 days at a temperature of 40° C. The apparatus was equippedwith a xenone lamp and provided an intensity of irradiation of 765 W/m²maximum. Twice daily, the containers were opened for 15 minutes in eachcase to allow air to enter. After the exposure, the residual content ofthe pheromone E,E-8,10-dodecadienol in the formulations according toinvention was analyzed and the data used to calculate the percentagedation. The results are compiled in Table 3.

TABLE 3 Example No. Pheromone degradation (%) 1 14.0 2 14.2 3 14.5 418.6 5 21.3 6 18.2

Example 7

0.03 g of E,E-8,10-dodecadienol, 0.04 g of butylhydroxytoluene, 2.0 g of2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate, 2.0 g of2-hydroxy-4-methoxy-ophenone and 3.5 g of cyfluthrin are dissolved in 22g of castor oil at 50° C. With the aid ofL a rotor/stator dispersingrod, this premix is emulsified at room temperature in a solution of 0.6g of a castor oil ethoxylate of a mean degree of ethoxylation of 30 in30 g of demineralized water. This emulsion is treated with of a 45% byweight aqueous dispersion of an emulsion polymer of acrylonitrile,buitadiene and methacrylic acid and with 7.43 g of demineralized waterwith stirring at room temperature. 2.5 g of hydroxyethylcellulose aresubsequently stirred in. (This hydroxyethylcellulose has a dynamicviscosity of 4000 mPa.S at 20° C. at a concentration of 20 g/l inwater.) After the mixture has been left to stand for 15 hours, it isstirred to give a homogeneous paste.

Comparison Example 1

2 g of the pheromone E,E-8,10-dodecadienol are dissolved at 50° C. in 98g of the absorber 2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate.

Comparison Example 2

2 g of the pheromone E,E-8,10-dodecadienol are dissolved at 50° C. in amixture of 73 g of 2-ethylliexyl 2-cyano-3,3-diphenyl-2-propenoate and25 g of 2-hydroxy-4-methoxy-benzophenol.

Comparison Example 3

3 g of the pheromone E,E-8,10-dodecadienol are dissolved at 50° C. in amixture of 25 g of the benzotriazole of Example 6 and 73 g of a paraffinoil of boiling point >300° C. and a viscosity of 16 mm²/sec.

Comparison Example 4

2 g of the pheromone E,E-8,10-dodecadienol are dissolved at 50° C. in 98g of castor oil.

Pheromone Stability Assessment

The formulations of the Comparison Examples 1 to 4 were tested forpheromone degradation with exposure to UV as has been described abovefor the compositions of Examples 1 to 6. The results are compiled inTable 4.

TABLE 4 Comparison Example No. Pheromone degradation (%) 1 96.3 2 87.4 398.0 4 99.9

Comparison Example 5

0.04 g of butylhydroxytoluene, 2.0 g of 2-ethylhexyl2-cyano-3,3-diphenyl-2-propenoate, 2.0 g of2-hydroxy-4-methoxy-benzophenone and 3.5 g of cyfluthrin are dissolvedin 22 g of castor oil at 50° C. With the aid of a rotor/statordispersing rod, this premix is emulsified at room temperature in asolution of 0.6 g of a castor oil ethoxylate of a mean degree ofethoxylation of 30 in 30 g of demineralized water. This emulsion istreated with 30 g of a 45% by weight aqueous dispersion of an emulsionpolymer of acrylonitrile, butadiene and methacrylic acid and with 7.43 gof demineralized water with stirring at room temperature. 2.5 g ofhydroxyethylcellulose are subsequently stirred in. (Thishydroxyethylcellulose has a dynamic viscosity of 4000 mPa.S at 20° C. ata concentration of 20 g/l in water.) After the mixture has been left tostand for 15 hours, it is stirred to give a homogeneous paste.

Use Examples Example A

Young apple trees of approximately 30 cm in size were treated on thestem, on one leaf on the upper side and on one leaf on the undersidewith the formulation according to the invention of Example 7 in the formof three drops approximately 50 microliters in size. The young treestogether with 10 male specimens of the codling moth (Cydia pomonella)were shut into gauze cages. Four of these cages were positioned in awind tunnel through which air was passed at a speed of 0.1 m/s. After 24hours, the total of destroyed insects in the cages was determined. Itwas 50% of the animals originally introduced. In an experiment with thepheromone-free comparison formulation 5 which was carried outsimultaneously, the percentage was only 12.5.

What is claimed is:
 1. A pesticidal composition comprising the followingingredients: a) 0.01 to 1 percent by weight of a signal substance havinga solubility in water of less than 1 gram per liter or a mixture of suchsignal substances, said signal substance being selected from the groupconsisting of pheromones, kairomones, and attractants; b) 1 to 40percent by weight of a UV absorber or a mixture of UV absorbers selectedfrom the group consisting of: i) a benzotriazole of the formula:

wherein R³ represents methyl or C₂-C₁₂-alkyl; ii)2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate of the formula:

iii) 2-hydroxy-4-methoxy-benzophenone of the formula:

c) 40 to 90 percent by weight of castor oil; d) a pesticidally effectiveamount of up to 10 percent by weight of at least one pyrethroid or amixture of pyrethroids; and e) optionally 0 to 70 percent by weight ofone or more additives selected from the group consisting of polymers,surface-active substances, colorants, antioxidants, thickeners, fillers,antifreeze agents, solvents and water; wherein the percents by weightare based on the weight of the composition after deducting the weight ofany water present therein.
 2. A pesticidal composition as claimed inclaim 1, wherein the UV absorber is2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate of the formula:

or 2-hydoxy-4-methoxy-benzophenone of the formula:

or a mixture of 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate and2-hydroxy-4-methoxy-benzophenone.
 3. A pesticidal composition as claimedin claim 1, wherein, after deducting the water which is present, thecontent of signal substance or signal substance mixture is between 0.05and 0.3% by weight.
 4. A pesticidal composition as claimed in claim 1,wherein, after deducting the water which is present, the content of UVabsorber or UV absorber mixture is between 5 and 20% by weight.
 5. Apesticidal composition as claimed in claim 1, wherein, after deductingthe water which is present, the content of castor oil is between 40 and85% by weight.
 6. A pesticidal composition as claimed in claim 1,wherein, after deducting the water which is present, the content ofpesticidally active compound or mixture of pesticidally active compoundsis up to 5% by weight.
 7. A pesticidal composition as claimed in claim1, wherein, after deducting the water which is present, the content ofadditives is between 0 and 60% by weight.
 8. A pesticidal composition asclaimed in claim 1, wherein, after deducting the water which is present,the content of: a) signal substance or signal substance mixture isbetween 0.05 and 0.3% by weight; b) UV absorber or UV absorber mixtureis between 5 and 20% by weight; c) castor oil is between 40 and 85% byweight; d) pesticidally active compound or a mixture of pesticidallyactive compound is up to 5% by weight; and e) additives is between 0 and60% by weight.
 9. A pesticidal composition as claimed in claim 1,wherein the pesticidally active compound is cyfluthrin.
 10. A pesticidalcomposition as claimed in claim 1, wherein the pesticidally activecompound is β-cyfluthrin.
 11. A pesticidal composition as claimed inclaim 1, wherein the signal substance is E,E-8,10-dodecadienol.
 12. Apesticidal composition as claimed in claim 1, wherein the UV absorber isa benzotriazole of the formula

in which R³ represents methyl or C₂-C₁₂-alkyl.
 13. Method forcontrolling harmful insects and undesirable representatives of the orderAcarina in agriculture, forestry and horticulture, which methodcomprises applying a composition as claimed in claim 1 to the habitat ofsaid harmful insects and undesirable representatives of the orderAcarina.